CHEMICAL OXIDATION

• Chemical oxidation in waste water treatment

involves the use of oxidizing agents such as
Ozone ( O3), Hydrogen peroxide
(H2O2),permanganate (MnO4), chlorine (Cl2)
and (O2) to bring about change in the chemical
composition of a compound or a group of
compounds.
FUNDAMENTALS OF CHEMICAL OXIDATION

• Oxidation – reduction reactions

• Half reaction potential
• Reaction potentials
• Equilibrium constants for redox equations
• Rate of Oxidation- Reduction reactions
 OXIDATION –REDUCTION REACTIONS
• An oxidation-reduction (redox) reaction is a type of
chemical reaction that involves a transfer of
electrons between two species.
• An oxidation-reduction reaction is any chemical
reaction in which the oxidation number of a
molecule, atom, or ion changes by gaining or losing
an electron.
• Redox reactions are common and vital to some of
the basic functions of life, including photosynthesis,
respiration, combustion, and corrosion or rusting.
 OXIDATION
• The term oxidation was originally used to
describe reactions in which an element
combines with oxygen
 OXIDATION EXAMPLE
• The reaction between magnesium metal and
oxygen to form magnesium oxide involves
the oxidation of magnesium
 REDUCTION
• The term reduction comes from the Latin
stem meaning "to lead back." Anything that
that leads back to magnesium metal
therefore involves reduction
 REDUCTION EXAMPLE
• The reaction between magnesium oxide and
carbon at 2000C to form magnesium metal
and carbon monoxide is an example of the
reduction of magnesium oxide to magnesium
metal.
• After electrons were discovered, chemists
became convinced that oxidation-reduction
reactions involved the transfer of electrons
from one atom to another. From this
perspective, the reaction between
magnesium and oxygen is written as follows
• In the course of this reaction, each
magnesium atom loses two electrons to form
an Mg2+ ion
• And, each O2 molecule gains four electrons to
form a pair of O2- ions
• Because electrons are neither created nor
destroyed in a chemical reaction, oxidation
and reduction are linked. It is impossible to
have one without the other, as shown in the
figure below.
 Rules for Assigning Oxidation States

• The oxidation state (OS) of an element

corresponds to the number of electrons, e ,
that an atom loses, gains, or appears to use
when joining with other atoms in compounds.
In determining the oxidation state of an atom,
there are seven guidelines to follow:
1.The oxidation state of an individual atom is 0.
2.The total oxidation state of all atoms in: a
neutral species is 0 and in an ion is equal to
the ion charge.
3. Group 1 metals have an oxidation state of +1
and Group 2 an oxidation state of +2
4.The oxidation state of fluorine is -1 in
compounds
5.Hydrogen generally has an oxidation state of
+1 in compounds
6.Oxygen generally has an oxidation state of -2
in compounds
7.In binary metal compounds, Group 17
elements have an oxidation state of -1, Group
16 elements of -2, and Group 15 elements of
-3.
The sum of the oxidation states is equal to zero
for neutral compounds and equal to the
charge for polyatomic ion species.
 Example : Assigning Oxidation States

• Determine the Oxidation States of each

element in the following reactions:
 SOLUTION -A
• Fe and O are free elements; therefore, they
each have an oxidation state of 0 according to
Rule #1. The product has a total oxidation
state equal to 0, and following Rule #6, O has
an oxidation state of -2, which means Fe has
an oxidation state of +3.
 SOLUTION -B
• The oxidation state of Fe corresponds to its
charge; therefore, the oxidation state is +2
 SOLUTION-C
• Ag has an oxidation state of 0, H has an
oxidation state of +1 according to Rule #5, S
has an oxidation state of -2 according to Rule
#7, and hence Ag in Ag S has an oxidation
state of +1.
Half-Reactions
• A half reaction is either the oxidation or
reduction reaction component of a redox
reaction.
• A half reaction is obtained by considering the
change in oxidation states of individual
substances involved in the redox reaction.
• Often, the concept of half-reactions is used to
describe what occurs in an electrochemical
cell, such as a Galvanic cell battery.
• Half-reactions can be written to describe both
the metal undergoing oxidation (known as the
anode) and the metal undergoing reduction
(known as the cathode).
• Half-reactions are often used as a method of
balancing redox reactions. For oxidation-
reduction reactions in acidic conditions, after
balancing the atoms and oxidation numbers,
one will need to add H ions to balance the
hydrogen ions in the half reaction.
• For oxidation-reduction reactions in basic
conditions, after balancing the atoms and
oxidation numbers, first treat it as an acidic
solution and then add OH ions to balance the
H ions in the half reactions (which would give
H O).
Example: Zn and Cu Galvanic cell
 PROBLEM-1 REF METCALF PG 520

Determine whether hydrogen sulfide (H2O) can

be oxidized with hydrogen peroxide (H2O2).
The pertinent half reactions from table 6.12
are as follow
H2S S + 2H+ + 2e- E0 = - 0.14
H2O2 + 2H+ + 2e- 2H2O E0 = + 1.776
• E0 Reaction = E0 Reduction - E0 Oxidation

• Where
E0 Reaction = Potential of the overall reaction
E0 Reduction = Potential of the reduction half
reaction
E0 Oxidation = Potential of the oxidation half
reaction
• The positive value of the E0Reaction Indicated that
the reaction will be proceed.

• The Negative value of the E0Reaction Indicated

that the reaction will be proceed in the
opposite.
 The Role of Oxidation Numbers in
Oxidation-Reduction Reactions
• Chemists eventually extended the idea of
oxidation and reduction to reactions that do
not formally involve the transfer of electrons.
Consider the following reaction.
• As can be seen in the figure below, the total
number of electrons in the valence shell of
each atom remains constant in this reaction
• What changes in this reaction is the oxidation
state of these atoms. The oxidation state of
carbon increases from +2 to +4, while the
oxidation state of the hydrogen decreases
from +1 to 0.
• Oxidation and reduction are therefore best
defined as follows. Oxidation occurs when
the oxidation number of an atom becomes
larger. Reduction occurs when the oxidation
number of an atom becomes smaller
 Oxidation State Rules
• To effectively assign oxidation states to a
compound, the seven basic rules must be
followed in order. Remember to use the rule
that comes first if two rules conflict with each
other. These rules hold true for most
compounds
 RULE 1
• Any individual atom uncombined with other
elements has the oxidation state of 0 (zero)

• Ex The Oxidation State for Ag is 0. The

oxidation state for O (oxygen) or O2 is 0 as long
as it is uncombined with any other element.
 RULE 2
• The total sum of the oxidation state of all atoms in any
given species is equal to the net charge on that species.

Example
• In neutral species, the total sum of the oxidation state
of all atoms is 0